US7117109B2ExpiredUtilityA1

Procedure for processing measuring data and device to perform the process

Assignee: AGILENT TECHNOLOGIES INCPriority: Jan 30, 2002Filed: Jun 26, 2002Granted: Oct 3, 2006
Est. expiryJan 30, 2022(expired)· nominal 20-yr term from priority
Inventors:Hubert Kuderer
G01N 30/8665G01N 2030/625
57
PatentIndex Score
2
Cited by
8
References
19
Claims

Abstract

A method for processing measuring data and a device to perform the method, wherein the measuring data can be determined by using a measurement system, more particularly a chromatographic analyzing system, for the measurement of measuring values that correspond to certain information about, or of, a technical process and that depend on at least two variables.

Claims

exact text as granted — not AI-modified
1. A method for processing measuring data from a measuring system, wherein the method comprises:
 a) calibrating the measuring system, wherein said calibrating includes:
 a 1 ) stimulating the measuring system by changing cause variables responsible for systematic measuring errors of the measuring system, and determining corresponding measuring data; and 
 a 2 ) determining effect vectors corresponding to systematic measuring errors from the measuring data obtained in step a 1 ) by using a mathematical method, wherein the effect vectors are based on a mathematical model with which the measuring data is estimated, wherein the mathematical model contains an error term containing an effect vector assigned to a measuring error and a corresponding error contribution; 
 
 b) measuring, using the measuring system, wherein said measuring includes:
 b 1 ) obtaining measuring data that corresponds to information concerning a process, while the process is taking place, and that depends on at least two variables; and 
 b 2 ) transforming the measuring data gathered in step b 1 ) to linear components, based on the effect vectors determined in step a 2 ), 
 b 3 ) using a mathematical method that corrects said transformed measuring data from step b 2 ) for said systematic measuring errors; and 
 b 4 ) outputting the corrected transformed measuring data from step b 3 . 
 
 
   
   
     2. A method according to  claim 1 , wherein said information is determined from the measuring of data by application of mathematical algorithms on which the mathematical model is based, by taking into account the error contributions. 
   
   
     3. A method according to  claim 1 ,
 wherein the mathematical model, for measuring of data dependent on two variables representing certain measuring values, is based on the following equation: 
 
     
       
         
           
             
               M 
               ⁢ 
               
                   
               
               ⁢ 
               
                 W 
                 
                   a 
                   , 
                   b 
                 
               
             
             = 
             
               
                 kn 
                 · 
                 
                   
                     ∑ 
                     
                       i 
                       = 
                       1 
                     
                     p 
                   
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     
                       NB 
                       
                         a 
                         , 
                         i 
                       
                     
                     · 
                     
                       NV 
                       
                         i 
                         . 
                         b 
                       
                     
                   
                 
               
               + 
               
                 kf 
                 · 
                 
                   
                     ∑ 
                     
                       j 
                       = 
                       1 
                     
                     q 
                   
                   ⁢ 
                   
                     
                       FB 
                       
                         a 
                         , 
                         j 
                       
                     
                     · 
                     
                       FV 
                       
                         j 
                         , 
                         b 
                       
                     
                   
                 
               
               + 
               
                 R 
                 
                   a 
                   , 
                   b 
                 
               
             
           
         
       
       wherein Mw a,b  is an measuring value, NB a,i  is a contribution of said information, NV i,b  is an effect vector corresponding to an information, FB a,j  is an error contribution, FV j,b  is an effect vector corresponding to systematic measuring errors, R a,b  is a residue, a and b are variables on which the measuring value depends, p is a number of carriers of information, q is a number of abstract error terms, and the scalars kn and kf are scaling factors for the contributions of information and the error contributions. 
     
   
   
     4. A method according to  claim 3 ,
 wherein the error contributions of the abstract effect vectors that correspond each to a systematic measuring error and which were determined according to step a 2 ), are determined for the measuring data obtained according to step b 1 ) over the variable a or b, for example the time, 
 wherein those values of the variable or those points in time are measured for which the residue exceeds a certain limit due to an effect of certain carriers of information and reaches the limit again after an interval of values or after a time interval, and 
 wherein subsequently the error contributions of the abstract effect vectors that correspond to systematic measuring errors are linearly interpolated for these values of the variables or for these points of time for the interval of values or the time interval in between so that the information which are corrected for systematical measuring errors in this interval of values or this time interval may be determined. 
 
   
   
     5. A method according to  claim 4 ,
 wherein estimated values of the information corrected for the systematic measuring errors by using the linearly interpolated error contributions, are determined according to the following equation: 
 
     
       
         
           
             
               SW 
               
                 a 
                 , 
                 b 
               
             
             = 
             
               
                 M 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 
                   W 
                   
                     a 
                     , 
                     b 
                   
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     
                       FB 
                       ′ 
                     
                     
                       a 
                       , 
                       j 
                     
                   
                   · 
                   
                     FV 
                     
                       j 
                       , 
                       b 
                     
                   
                 
               
             
           
         
       
       wherein SW is an estimated value of the information, MW is an measuring value, FB′ are error contributions linearly interpolated over the values of the variables or the time, FV is an effect vector that corresponds to systematic measuring errors, a and b are variables on which the measuring value depends, and q represents a number of abstract error terms. 
     
   
   
     6. A method according to  claim 4 ,
 wherein for a chromatographic analyzing system designed as an absorption measuring system which generates measuring data in the form of absorption values according to the wavelength and the time, estimated values of the absorption values which are corrected for systematical measuring errors are determined by using linearly interpolated error contributions, by using the following equation: 
 
     
       
         
           
             
               A 
               
                 t 
                 , 
                 λ 
               
             
             = 
             
               
                 M 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 
                   W 
                   
                     t 
                     , 
                     λ 
                   
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     k 
                     
                       t 
                       , 
                       j 
                     
                     ′ 
                   
                   · 
                   
                     Spec 
                     
                       j 
                       , 
                       λ 
                     
                   
                 
               
             
           
         
       
       wherein A is an estimated value of the absorption, MW is an measuring value, k′ are error contributions interpolated linearly over time, Spec is an effect vector corresponding to systematic measuring errors, t and λ represent the variables time and wavelength, respectively, on which the measured absorption values depend, and q is a number of abstract error terms. 
     
   
   
     7. A method according to  claim 4 ,
 wherein an effect vector corresponding to the information of the carrier of information causing the effect is determined by using the linearly interpolated error contributions at a point where the residue reaches a maximum value and by applying the following equation: 
 
     
       
         
           
             
               NV 
               
                 i 
                 , 
                 b 
               
             
             = 
             
               
                 M 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 
                   W 
                   
                     
                       a 
                       i 
                     
                     , 
                     b 
                   
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     FB 
                     
                       
                         a 
                         i 
                       
                       , 
                       j 
                     
                     ′ 
                   
                   · 
                   
                     FV 
                     
                       j 
                       , 
                       b 
                     
                   
                 
               
             
           
         
       
       wherein NV i,b  is an effect vector of the carrier i of information, MV ai,b  is an measuring value, FB′ aj,j  are linearly interpolated error contributions, FV j,b  is an effect vector corresponding to the systematic measuring errors, and a and b are variables, on which the measuring value depends, and 
       wherein the effect vector corresponding to the information of the carrier of information determined in this manner is added to the abstract effect vectors corresponding to the systematic measuring errors and determined according to step a 2 ), and 
       wherein subsequently the effect vector contributions of these effect vectors are determined with which the information can be determined by using a mathematical method. 
     
   
   
     8. A method according to  claim 7 ,
 wherein estimated values of the information, which have been corrected for systematic measuring errors, are determined by using effect vector contributions and by applying the following equation:
     SW   a,b,i   =NB″   a,i   ·NV   i,b   
 
 wherein SW a,b,i  are real estimated values of the information of the carrier i depending on the variables a and b, NB″ a,i  are effect vector contributions, and NV i,b  is an effect vector of the carrier i of information. 
 
   
   
     9. A method according to  claim 4 ,
 wherein, in the interval of values or in the time interval in which the residue exceeds a certain limit and reaches the limit again after an interval of values or a time interval caused by the superposition of several carriers of information, all contributions of information and all systematic error contributions contributing to the corresponding measuring values are determined, and 
 wherein the estimated values of the real information, which have been corrected for systematic measuring errors by using the linearly interpolated error contributions, are first determined and then the effect vectors that correspond to the information of all carriers of information are calculated by using a mathematical method and 
 wherein theses effect vectors are subsequently added to the error effect vectors corresponding to the systematic measuring errors, and 
 wherein for all effect vectors, their effect vector contributions are subsequently determined using a mathematical method and 
 wherein the effect vector contributions can be used to determine the information and the systematic measuring errors. 
 
   
   
     10. A method according to  claim 4 ,
 wherein for a chromatographic analyzing system designed as an absorption measuring system which generates measuring data in the form of absorption values according to the wavelength and the time, a spectrum of the substance causing the effect is determined by using linearly interpolated error contributions at a point of time where the residue reaches a maximum value and by applying the following equation: 
 
     
       
         
           
             
               ɛ 
               
                 x 
                 , 
                 λ 
               
             
             = 
             
               
                 MW 
                 
                   
                     t 
                     x 
                   
                   , 
                   λ 
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     k 
                     
                       
                         t 
                         x 
                       
                       , 
                       j 
                     
                     ′ 
                   
                   · 
                   
                     Spec 
                     
                       j 
                       , 
                       λ 
                     
                   
                 
               
             
           
         
       
       wherein ε x,1  is a spectrum of the substance x causing the effect, MW  t     x      λ  is a measured absorption spectrum at a time t x  over the wavelength λ, k′ t     x    j are error contributions of j abstract effect vectors Spec j,λ  over the wavelength λ at the time t x,  and 
       wherein the spectrum determined in this manner is added to the abstract effect vectors that correspond to the systematic measuring errors and which are determined according to step a 2 ), and subsequently their effect vector contributions are determined for all effect vectors by using a mathematical method and 
       wherein these effect vector contributions can be used to determine the information corrected for systematic measuring errors. 
     
   
   
     11. A method according to  claim 10 ,
 wherein the estimated values of the absorption of the substance causing the effect (peak) are determined by using the effect vector contributions and by applying the following equation:
     A   t,λ,x   =K″   t,x   ·ε   x,λ   
 
 wherein A t,λx  are real estimated values of the information of the substance x, depending on the variables t and λ, k″ a,i  are effect vector contributions, and is a spectrum of the substance x. 
 
   
   
     12. A method according to  claim 3 ,
 wherein the error contributions of the abstract effect vectors that correspond each to a systematic measuring error and which were determined according to step a 2 ), are determined for the measuring data obtained according to step b 1 ) for the variable a or b, 
 wherein those values of the variables are determined for which the residue exceeds a certain limit due to an effect of certain carriers of information and reaches the limit again after an interval of values, and 
 wherein those error contributions are determined in a limited interval corresponding to one of the variables a or b, for which there is no information within the interval of values, and 
 wherein these error contributions are used to determine estimated values which are corrected for systematic measuring errors within the interval of values by using the following equation: 
 
     
       
         
           
             
               SW 
               
                 a 
                 , 
                 b 
               
             
             = 
             
               
                 M 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 
                   W 
                   
                     a 
                     , 
                     b 
                   
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     
                       FB 
                       ′ 
                     
                     
                       a 
                       , 
                       j 
                     
                   
                   · 
                   
                     FV 
                     
                       j 
                       , 
                       b 
                     
                   
                 
               
             
           
         
       
       wherein SW is an estimated value of the information, MW is an measuring value, FB′ are error contributions linearly interpolated over the values of the variables or the time, FV is an effect vector that corresponds to systematic measuring errors, a and b are variables on which the measuring value depends, and q represents a number of abstract error terms, for the complete interval of the variable a or b. 
     
   
   
     13. A method according to  claim 3 ,
 wherein for a chromatographic analyzing system designed as an absorption measuring system which generates measuring data in the form of absorption values according to the wavelength and the time, the error contributions of the abstract effect vectors that correspond each to a systematic measuring error and which were determined according to step a 2 ) are determined for the measuring data determined according to step b 1 ) over the time, 
 wherein those points in time were determined for which, due to an effect to a certain substance, the residue exceeds a certain limit and reaches the limit again after a time interval, and 
 wherein those error contributions are determined in a limited wavelength interval in which the substance to be studied does not absorb, and 
 wherein subsequently estimated values of the absorption, which are corrected for systematic measuring errors are determined by using these error contributions within the interval of time by applying the following equation: 
 
     
       
         
           
             
               A 
               
                 t 
                 , 
                 λ 
               
             
             = 
             
               
                 M 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 
                   W 
                   
                     t 
                     , 
                     λ 
                   
                 
               
               - 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     k 
                     
                       t 
                       , 
                       j 
                     
                     ′ 
                   
                   · 
                   
                     Spec 
                     
                       j 
                       , 
                       λ 
                     
                   
                 
               
             
           
         
       
       wherein A is an estimated value of the absorption, MW is an measuring value, k′ are error contributions interpolated linearly over time, Spec is an effect vector corresponding to systematic measuring errors, t and μ represent the variables time and wavelength respectively, on which the measured absorption values depend, and q is a number of abstract error terms, in the entire wavelength interval. 
     
   
   
     14. A method according to  claim 1 ,
 wherein the mathematical model which generates measuring data in the form of absorption values according to the wavelength and the time, is based on the following equation: 
 
     
       
         
           
             
               M 
               ⁢ 
               
                   
               
               ⁢ 
               
                 W 
                 
                   t 
                   , 
                   λ 
                 
               
             
             = 
             
               
                 d 
                 · 
                 
                   
                     ∑ 
                     
                       i 
                       = 
                       1 
                     
                     p 
                   
                   ⁢ 
                   
                     
                       c 
                       
                         t 
                         , 
                         i 
                       
                     
                     · 
                     
                       ɛ 
                       
                         i 
                         , 
                         λ 
                       
                     
                   
                 
               
               + 
               
                 
                   ∑ 
                   
                     j 
                     = 
                     1 
                   
                   q 
                 
                 ⁢ 
                 
                   
                     k 
                     
                       t 
                       , 
                       j 
                     
                   
                   · 
                   
                     Spec 
                     
                       j 
                       , 
                       λ 
                     
                   
                 
               
               + 
               
                 R 
                 
                   t 
                   , 
                   λ 
                 
               
             
           
         
       
       wherein MW is an absorption value varying with the time t and the wavelength λ, d is the layer length of a flux cell, c is the concentration of a substance i, i.e., a contribution of information of an effect vector characterizing information, in this case an extinction coefficient ε, k is an error contribution of the effect vector (Spec) corresponding to a systematic measuring error, R is a residue, p is a number of substances contributing to the absorption spectrum, and q represents a number of abstract error terms. 
     
   
   
     15. The method according to  claim 1 , wherein said outputting comprises storing said corrected transformed measuring data from step b 4 . 
   
   
     16. The method according to  claim 1 , further comprising deriving further data from said corrected transformed measuring data from step b 4 . 
   
   
     17. A device for processing measuring data from a measuring system, wherein said device, when coupled with the measuring system, performs a method comprising:
 a) calibrating the measuring system, wherein said calibrating includes:
 a 1 ) stimulating the measuring system by changing cause variables responsible for systematic measuring errors of the measuring system, and determining corresponding measuring data; and 
 a 2 ) determining effect vectors corresponding to systematic measuring errors from the measuring data obtained in step al) by using a mathematical method, wherein the effect vectors are based on a mathematical model with which the measuring data is estimated, wherein the mathematical model contains an error term containing an effect vector assigned to a measuring error and a corresponding error contribution; 
 
 b) measuring, using the measuring system, wherein said measuring includes:
 b 1 ) obtaining measuring data that corresponds to information conceming a process while the process is taking place, and that depends on at least two variables; and 
 b 2 ) transforming the measuring data gathered in step b 1 ) to linear components, based on the effect vectors determined in step a 2 ), 
 b 3 ) by using a mathematical method that corrects said transformed measuring data from step b 2 ) for said systematic measuring errors; and 
 b 4 ) outputting the corrected transformed measuring data from step b 3 . 
 
 
   
   
     18. The device according to  claim 17 , wherein said outputting comprises storing said corrected transformed measuring data from step b 4 . 
   
   
     19. The device according to  claim 17 , wherein said device further performs an activity of deriving further data from said corrected transformed measuring data from step b 4 .

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